CN106565958A - N, N-dimethyl dodecyl terminal quaternization modified silicone oil, and preparation method and application thereof - Google Patents
N, N-dimethyl dodecyl terminal quaternization modified silicone oil, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to N, N-dimethyl dodecyl terminal quaternization modified silicone oil, and a preparation method and application thereof. The preparation method comprises the steps of reacting octamethyl cyclotetrasiloxane and tetramethyl dihydro disiloxane according to the proportion in the presence of an acid catalyst so as to prepare double-terminal hydrogenous silicon oil; carrying out hydrosilylation reaction on the silicon oil and glycidyl allyl ether or allyl polyoxyethylene polyoxypropylene glycidyl ether to obtain epoxy-terminated silicone oil; and finally, carrying out aminolysis ring-opening reaction on the epoxy-terminated silicone oil and N, N-dodecyl tertiary amine to obtain the terminal quaternization modified silicone oil. The silicone oil is used as a textile finishing agent for treating cotton fabrics, so that the cotton fabrics are endowed with an antibacterial property, meanwhile, the softness of the cotton fabrics can be also improved, and the hydrophilia is better at the same time.
Description
Technical field
The present invention relates to modified block silicone oil, and in particular to a kind of quaternised modified silicon in N, N- dimethyl dodecyl base end
Oil and its preparation method and application.
Background technology
At present for quaternised modified silicone oil is much studied, except soft with providing on the strand of this silicone oil
Outside the PolydimethylsiloxaneChain Chain section of property, the quaternary amines of also appropriate cationization can give fabric certain antibiotic property,
Moisture absorption antistatic behaviour etc..Its Antibacterial Mechanism is adsorbed in microbial cell surface by quaternary amines, makes zymoprotein and core
There is degeneration in acid, destroy its enzyme system, damaging cells film.Compared to commercially available organosilicon antibacterial agent, such as (trimethoxy silicon substrate third
Base) octadecyldimethyl ammonium chloride etc., quaternised modified silicone oil has regulatable polysiloxanes segment and quaternary amine base simultaneously
Group, it is common to realize soft and antibiotic finish, with good stability, it is not volatile the features such as, and (trimethoxy silicon substrate propyl group) ten
Eight alkyl dimethyl ammonium chlorides do not have polysiloxanes segment, can only give antibacterial fabric.Therefore, this quaternized change is prepared
Property silicone oil there is certain realistic meaning, also have many researchs to it both at home and abroad.
Li Junying etc. (synthesis of polysiloxane quaternary ammonium and its antibiotic property, daily chemical industry) adopts mass polymerization,
It is prepared for first containing N, the tertiary amine groups silicone oil of N- diethyl-aminopropyl, then it is occurred into quaterisation with benzyl chloride, is obtained
Polysiloxane quaternary ammonium, experiment finds that this quaternary sillicones have to escherichia coli and mycete certain suppression make
With, when polysiloxane quaternary ammonium aqueous solution mass fraction be more than 0.5% when, 100% has been reached to colibacillary bacteriostasis rate.
Huang Zuoxin etc. (antibacterial activity of quaternary ammonium salt base polysiloxanes, textile journal, Huang is made prosperous etc.) have studied with benzyl dimethyl silicon
The polysiloxanes of propyl ammonium chloride side base, as a result show its bactericidal activity to escherichia coli and staphylococcus aureuses very
By force, when the mass concentration of this quaternized silicone oil is more than 1.5%, its adsorbance on cotton reaches saturation, and bacteriostasis rate is most
Height, reaches 100%.
Divide positioned at the position of macromolecular chain according to quaternary amines, quaternised modified silicone oil mainly has side chain type, and (pectination is tied
Structure), tip type, main chain block type this several class.The quaternized silicone oil of side chain type can be by quaternizing agent and traditional amino
Silicone oil reaction is obtained, such as (the Modification of Surface Properties of such as Somasundaran, P.
Cellulosic Substrates by Quaternized Silicone Emulsions.J.Colloid Interface
Sci.Purohit,P.S.；Somasundaran, P.) carried out with methyl tosylate and γ-aminopropyl silicone oil it is quaternary ammoniated anti-
Should, the quaternary amine silicone oil of side chain type is obtained, as a result show that this quaternary amine silicone oil can effectively reduce the coefficient of friction of fabric face, give
Fabric sofetening smooth hand.The quaternized silicone oil of main chain block type can be obtained by there is quaterisation to block silicone oil,
Such as pacify Qiu Feng etc. (synthesis of quaternized polyether block polysiloxanes and sign, printing and dyeing assistant) and prepare epoxy radicals polyethers envelope first
The polydimethylsiloxane at end, then itself and tetramethylethylenediamine generation opening are obtained into the poly- silicon of quaternized polyether block
Oxygen alkane.
But in prior art, for the quaternary amine silicone oil of side chain type, when using mass polymerization synthesizing amino silicone oil then right
When it carries out quaterisation preparation, the distribution of the quaternary ammonium group of side chain is often uneven, is easily caused emulsion unstability, and this
Even if kind of silicone oil is when quaternization degree is very low, still with very big viscosity, storage and emulsifying are difficult.For many block type silicon
Oil, its viscosity can become much larger with the increase of molecular weight, when controlling bad, can usually obtain gel-like product, sometimes product
Gelation also can occur during storage.
The content of the invention
Present invention aims to the deficiencies in the prior art, there is provided a kind of N, N- dimethyl dodecyl base end quaternary ammonium
Change modified silicon oil and its preparation method and application, the silicone oil is processed after bafta as fabric finishing agent, anti-in providing cotton fabric
While bacterium property, the flexibility of fabric can be also improved；Secondly so that the whiteness and water absorption of bafta is also preferable.
Technical scheme provided by the present invention is：
A kind of quaternised modified silicone oil in N, N- dimethyl dodecyl base end, the compound containing structure as shown in formula I：
In formula I, it is that 0～5, b is 0～20 that n is 7～100, a.
In above-mentioned technical proposal, the skeleton symbol of the quaternised modified silicone oil in N, N- dimethyl dodecyl base end is ABA, its
Middle A is quaternary amines, and B is polysiloxanes segment.The advantage of this three block type structure silicone oil is that the viscosity of copolymer can be with
Regulation and control are not susceptible to gel, it may have more regular structure, it is ensured that all have quaternary amine on most of strand in rational scope
Group.Reason is N, the N in the quaternised modified silicone oil in N- dimethyl dodecyl bases end, N- dimethyl dodecyl base quaternary ammonium groups
Group and polyether segment are respectively positioned on high molecular main chain, and the silicone oil of this backbone modification has more regular structure, on the one hand,
The emulsifying capacity and stability of emulsion of silicone oil can be improved, on the other hand, the hydrophilic of fabric after arranging can be improved, be resisted quiet
Electrical property etc..
The present invention also provides a kind of N described above, the preparation side of the quaternised modified silicone oil in N- dimethyl dodecyl bases end
Method, comprises the steps：
1) octamethylcy-clotetrasiloxane and hydrogeneous double-seal head carry out polyreaction under acidic catalyst effect, obtain end and contain
Hydrogen silicone oil；
The structure of the end containing hydrogen silicone oil is as shown in formula II：
In formula II, n is 7～100；
2) by step 1) in the end containing hydrogen silicone oil that obtains and allyl glycidyl ether or allyl polyethenoxy polyoxy third
Alkene glycidyl ether carries out hydrosilylation, obtains holding epoxy silicon oil；
The structure of the end epoxy silicon oil is as shown in formula III：
In formula III, it is that 0～5, b is 0～20 that n is 7～100, a；
3) by step 2) in the end epoxy silicon oil that obtains and N, N- dimethyl dodecylamine and acetic acidreaction, obtain described
The quaternised modified silicone oil in N, N- dimethyl dodecyl base end.
The step 1) in reaction carry out under conditions of solvent-free participation, octamethylcy-clotetrasiloxane and hydrogeneous double-seal head
Generation polymerisation in bulk obtains product, after reaction is completed, catalyst is filtered to remove, then is by vacuum distillation removing low boiling
Can obtain holding containing hydrogen silicone oil.
The step 1) in hydrogeneous double-seal head structure as shown in formula IV：
Preferably, the step 1) in acidic catalyst be Emathlite or H2SO4.The quality of the acidic catalyst
For the 0.5～4% of reactant liquor quality.The reactant liquor refers to the hybrid reaction of octamethylcy-clotetrasiloxane and hydrogeneous double-seal head
Liquid.
Preferably, the step 1) in octamethylcy-clotetrasiloxane and hydrogeneous double-seal head mass ratio be 4～75:1.
Preferably, the step 1) in reaction temperature be 60～80 DEG C, the response time be 5～24h.
The step 2) in reaction carry out under conditions of solvent-free participation, end containing hydrogen silicone oil and allyl glycidyl ether
Or allyl polyethenoxy polyoxypropylene glycidyl ether carries out hydrosilylation under chloroplatinic acid or Karst catalyst, instead
After should completing, slightly excessive polyether reactant thing is removed by vacuum distillation or methanol extraction washing, you can obtain end ring oxygen silicon
Oil.
The step 2) in allyl glycidyl ether structure such as formula (V) shown in：
The step 2) in allyl polyethenoxy polyoxypropylene glycidyl ether structure as shown in formula VI：
Wherein, the molecular weight of allyl polyethenoxy polyoxypropylene glycidyl ether be 600～2000g/mol, a=0～
5, b=0～20, preferably 600～1000g/mol.
Preferably, the step 2) in catalyst consumption for containing hydrogen silicone oil 10-100ppm, with platinum and si-h bond
Molal quantity is calculated.
Preferably, the step 2) middle-end containing hydrogen silicone oil and allyl glycidyl ether or allyl polyethenoxy polyoxy
The mol ratio of propylene glycidyl ether is 1:2～2.2.
Preferably, the step 2) in reaction temperature be 60～90 DEG C, the response time be 3～12h.
The step 3) in N, shown in the structure such as formula (VII) of N- dimethyl dodecylamines：
Preferably, the step 3) in reaction temperature be 60～90 DEG C, the response time be 3～12h.
The present invention also provides a kind of N described above, and the quaternised modified silicone oil in N- dimethyl dodecyl bases end is knitted in preparation
Application in thing finishing agent.
The application process includes：Using inversed phase emulsification, under agitation, to the N, N- dimethyl dodecyls base end
Hold and sequentially add in quaternised modified silicone oil composite emulsifier, aqueous acetic acid, obtain the water-in-oil emulsion of homogeneous transparent, continue
Water is added, the N of homogeneous transparent, the quaternised modified silicone oil emulsion in N- dimethyl dodecyl bases end is obtained.
Preferably, the application in fabric softener or antibacterial finishing agent is prepared.
Preferably, the composite emulsifier is fatty alcohol polyethenoxy ether class emulsifying agent；More preferably, AEO-3
With AEO-9 with mass ratio as 1:0.1～10 ratio compounding, the emulsifying agent is purchased from Zhejiang Jilida Chemical Co., Ltd；It is described
Composite emulsifier consumption is the N, 0～50wt.% of the quaternised modified silicone oil in N- dimethyl dodecyl bases end.
Preferably, the concentration of described aqueous acetic acid is 8～10wt.%.
Compared with the existing technology, beneficial effects of the present invention are embodied in：
(1) skeleton symbol of the quaternised modified silicone oil in N provided by the present invention, N- dimethyl dodecyl base end is ABA,
Wherein A is quaternary amines, and B is polysiloxanes segment.The advantage of this three block type structure silicone oil is that the viscosity of copolymer can
To regulate and control in rational scope, gel is not susceptible to, it may have more regular structure, it is ensured that all have season on most of strand
Amine groups.
(2) the quaternised modified silicone oil in N provided by the present invention, N- dimethyl dodecyl base end, polyether segment and N, N-
Dimethyl dodecyl base quaternary ammonium group is respectively positioned on high molecular main chain, and structure is more regular, it is ensured that contained on most of strand
The modified silicon oil for having quaternary amines, this compound with regular structure is easier to make for can emulsifying, be also beneficial to stablizing for emulsion.This
Outward, the modest viscosity of this terminal-modified type silicone oil, and how block modified silicone oil is easy in gel.
(3) the quaternised modified silicone oil in N provided by the present invention, N- dimethyl dodecyl base end as fabric finishing agent at
After reason bafta, while providing cotton fabric antibiotic property, the flexibility of fabric can be also improved；Secondly so that bafta it is white
Degree and water absorption are also preferable.
Description of the drawings
Fig. 1 is N in embodiment 3, the nuclear magnetic spectrogram (1H NMR) of the quaternised modified silicone oil in N- dimethyl dodecyl bases end；
Fig. 2 is N in embodiment 6, the nuclear magnetic spectrogram (1H NMR) of the quaternised modified silicone oil in N- dimethyl dodecyl bases end；
Fig. 3 is the building-up process schematic diagram of silicone oil in embodiment 1～3；
Fig. 4 is the building-up process schematic diagram of silicone oil in embodiment 4～6.
Specific embodiment
With reference to embodiment and Figure of description, the present invention is described further.
Embodiment 1
Octamethylcy-clotetrasiloxane (D4), hydrogeneous double-seal head and acidity of catalyst hargil solid in mass ratio 100:24.54:
During 2.5 are added to equipped with magnetic agitation, thermometer, the there-necked flask of condensing tube, stirring in a nitrogen atmosphere is warming up to 65 DEG C instead
Answer 24h.System viscosity becomes big after end, Filtration of catalyst, and the vacuum distillation at 100 DEG C removes low-boiling-point substance, obtains colourless
The end containing hydrogen silicone oil of transparent products, as molal weight 680g/mol or so, is labeled as PHMS1.
By end containing hydrogen silicone oil PHMS1 and allyl polyethenoxy polyoxypropylene glycidyl ether (molal weight 700g/mol,
It is labeled as APE, industrial goods, by Zhejiang, passeris montani saturati screen weaving Chemical Co., Ltd. gives) by 1:2 mol ratio is added in flask,
Under nitrogen atmosphere, chloroplatinic acid (calculating with the mol ratio of the platinum and si-h bond) catalyst of 50ppm, stirring is added to be warming up to 80 DEG C,
After reaction 5h, colourless to lurid transparent products are obtained, as end ring oxygen polyether silicone oil, be labeled as PHMS1-APE.
By end ring oxygen polyether silicone oil PHMS1-APE, N, N- dimethyl dodecylamine and acetic acid press 1:2:2 mol ratio adds
In entering flask, nitrogen displacement, stirring is warming up to 80 DEG C of reaction 8h, after reaction terminates, obtains the larger light yellow clear of viscosity and produces
Thing, as N, the quaternised modified silicone oil in N- dimethyl dodecyl bases end is labeled as PHMS1-APE-AN, preparation process such as Fig. 3
It is shown.
Embodiment 2
Octamethylcy-clotetrasiloxane (D4), hydrogeneous double-seal head and acidity of catalyst hargil solid in mass ratio 100:3.56:
During 2.1 are added to equipped with magnetic agitation, thermometer, the there-necked flask of condensing tube, stirring in a nitrogen atmosphere is warming up to 65 DEG C instead
Answer 24h.System viscosity becomes big after end, Filtration of catalyst, and the vacuum distillation at 100 DEG C removes low-boiling-point substance, obtains colourless
The end containing hydrogen silicone oil of transparent products, as molal weight 3900g/mol or so, is labeled as PHMS2.
End containing hydrogen silicone oil PHMS2 and allyl polyethenoxy polyoxypropylene glycidyl ether are pressed into 1:2 mol ratio is added
To in flask, under nitrogen atmosphere, the chloroplatinic acid catalyst of 50ppm, stirring is added to be warming up to 80 DEG C, after reaction 8h, obtain nothing
To lurid transparent products, as end ring oxygen polyether silicone oil is labeled as PHMS2-APE to color.
By end ring oxygen polyether silicone oil PHMS2-APE, N, N- dimethyl dodecylamine and acetic acid press 1:2:2 mol ratio adds
In entering flask, nitrogen displacement, stirring is warming up to 80 DEG C of reaction 10h, after reaction terminates, obtains the larger light yellow clear of viscosity and produces
Thing, as N, the quaternary ammoniated modified silicon oil in N- dimethyl dodecyl bases end is labeled as PHMS2-APE-AN, preparation process such as Fig. 3
It is shown.
Embodiment 3
Octamethylcy-clotetrasiloxane (D4), hydrogeneous double-seal head and catalyst concentrated sulphuric acid in mass ratio 100:1.4:2 are added to
In equipped with magnetic agitation, thermometer, the there-necked flask of condensing tube, stirring in a nitrogen atmosphere is warming up to 65 DEG C of reaction 24h.Terminate
Afterwards system viscosity becomes big, adds in sodium bicarbonate and concentrated sulphuric acid, and stirring refilters removing solid after a period of time, finally 100
Vacuum distillation at DEG C removes low-boiling-point substance, obtains water white transparency product, as the end Silicon Containing Hydrogen of molal weight 9700g/mol or so
Oil, is labeled as PHMS3.
End containing hydrogen silicone oil PHMS3 and allyl polyethenoxy polyoxypropylene glycidyl ether are pressed into 1:2 mol ratio is added
To in flask, under nitrogen atmosphere, the chloroplatinic acid catalyst of 50ppm, stirring is added to be warming up to 80 DEG C, after reaction 8h, obtain nothing
To lurid transparent products, as end ring oxygen polyether silicone oil is labeled as PHMS3-APE to color.
By end ring oxygen polyether silicone oil PHMS3-APE, N, N- dimethyl dodecyl base and acetic acid press 1:2:2 mol ratio is added
In flask, nitrogen displacement, stirring is warming up to 80 DEG C of reaction 10h, after reaction terminates, obtains the larger light yellow clear of viscosity and produces
Thing, as N, the quaternary ammoniated modified silicon oil in N- dimethyl dodecyl bases end is labeled as PHMS3-APE-AN, preparation process such as Fig. 3
It is shown.
The N, the nuclear magnetic spectrogram 1H NMR of the quaternary ammoniated modified silicon oil in N- dimethyl dodecyl bases end of gained) as shown in Figure 1.
Embodiment 4
End containing hydrogen silicone oil PHMS1 (by preparing in embodiment 1) and allyl glycidyl ether (are labeled as AGE, are divided
Analysis is pure, pacifies resistance to Jilin Chemical) press 1:2.1 mol ratio is added in flask, and under nitrogen atmosphere, the chloroplatinic acid for adding 50ppm is urged
Agent, stirring is warming up to 80 DEG C, after reaction 8h, by vacuum distillation slightly excessive allyl glycidyl ether is removed, and obtains nothing
Color as holds epoxy silicon oil to lurid transparent products, is labeled as PHMS1-AGE.
By end epoxy silicon oil PHMS1-AGE, N, N- dimethyl dodecylamine and acetic acid press 1:2:2 mol ratio is added burns
In bottle, nitrogen displacement, stirring is warming up to 80 DEG C of reaction 10h, after reaction terminates, obtains the larger light yellow clear product of viscosity,
The quaternary ammoniated modified silicon oil in as N, N- dimethyl dodecyl base end, is labeled as PHMS1-AGE-AN, preparation process such as Fig. 4 institutes
Show.
Embodiment 5
By end containing hydrogen silicone oil PHMS2 (by preparing in embodiment 2) and allyl glycidyl ether by 1:2.1 mole
In than being added to flask, under nitrogen atmosphere, the chloroplatinic acid catalyst of 50ppm, stirring is added to be warming up to 80 DEG C, after reaction 8h,
Slightly excessive allyl glycidyl ether is removed by vacuum distillation, colourless to lurid transparent products, as end ring are obtained
Oxygen silicone oil, is labeled as PHMS2-AGE.
By end epoxy silicon oil PHMS2-AGE, N, N- dimethyl dodecylamine and acetic acid press 1:2:2 mol ratio is added burns
In bottle, nitrogen displacement, stirring is warming up to 80 DEG C of reaction 10h, after reaction terminates, obtains the larger light yellow clear product of viscosity,
The quaternary ammoniated modified silicon oil in as N, N- dimethyl dodecyl base end, is labeled as PHMS2-AGE-AN, preparation process such as Fig. 4 institutes
Show.
Embodiment 6
By end containing hydrogen silicone oil PHMS3 (by preparing in embodiment 3) and allyl glycidyl ether by 1:2.1 mole
In than being added to flask, under nitrogen atmosphere, the chloroplatinic acid catalyst of 50ppm, stirring is added to be warming up to 80 DEG C, after reaction 8h,
Slightly excessive allyl glycidyl ether is removed by vacuum distillation, colourless to lurid transparent products, as end ring are obtained
Oxygen silicone oil, is labeled as PHMS3-AGE.
By end epoxy silicon oil PHMS3-AGE, N, N- dimethyl dodecylamine and acetic acid press 1:2:2 mol ratio is added burns
In bottle, nitrogen displacement, stirring is warming up to 80 DEG C of reaction 10h, after reaction terminates, obtains the larger light yellow clear product of viscosity,
The quaternary ammoniated modified silicon oil in as N, N- dimethyl dodecyl base end, is labeled as PHMS3-AGE-AN, preparation process such as Fig. 4 institutes
Show.
The N of gained, the quaternary ammoniated modified silicon oil nuclear magnetic spectrogram in N- dimethyl dodecyl bases end (1H NMR) is as shown in Figure 2.
The emulsifying process of silicone oil
Before silicone oil is applied to into textile finishing, need first by 6 kinds of silicone oil emulsifications of the gained of embodiment 1～6 into emulsion.Specifically
Emulsifying process be, in round-bottomed flask add 10g silicone oil, 4g isopropanol solvents and 0～5g compounding aliphatic alcohol polyethenoxy
Ethers emulsifying agent (AEO-3 and AEO-9 compoundings are formed), wherein, PHMS1-APE-AN and PHMS2-APE-AN need not add emulsifying
Agent, it is possible to achieve self emulsifying (polysiloxanes segment is shorter), PHMS3-AGE-AN needs to add because polysiloxanes segment is longer
The emulsifying agent of 5g compoundings can just obtain the emulsion of clear stable.Silicone oil is stirred with the mixed liquor of emulsifying agent, then slowly
The aqueous acetic acid that is made up of 1g acetic acid and 9g water of addition, stirring can obtain uniform water-in-oil system, it is eventually adding 21～
26g water, stirs, and adjusts pH to 5.5-6, obtains the silicone oil emulsion of solid content 20% or so.
Bafta postfinishing process
Processed with laboratory room small-sized padding machine after Cotton Fabric.First silicone oil emulsion is diluted with water to into silicate-containing oil
For 1% work body lotion, then bafta impregnated in above-mentioned work body lotion (bath raio is 1：20) 30min, using padding machine to knitting
Thing carries out an immersing and rolling PROCESS FOR TREATMENT, then cloth specimen is dried into 2min at 80 DEG C, and at 130 DEG C 1min is dried.Cloth specimen after arrangement exists
Temperature be 25 ± 2 DEG C, relative humidity be 65% ± 2% under the conditions of balance 24h it is standby.
The cloth specimen that silicone oil in Jing embodiments 1～6 was processed is respectively labeled as PHMS1-APE-AN/cotton, PHMS2-
APE-AN/cotton, PHMS3-APE-AN/cotton, PHMS1-AGE-AN/cotton, PHMS2-AGE-AN/cotton,
PHMS3-AGE-AN/cotton。
Comparative example 1
Using untreated bafta as blank sample, cotton is labeled as, determines properties.
Comparative example 2
With commercially available organosilicon antibacterial agent, (trimethoxy silicon substrate propyl group) octadecyldimethyl ammonium chloride, as a comparison,
Structure is shown below：
The application performance test of bafta after arrangement
The flexibility of bafta is tested using LLY-01B type electronics hardometer.Test result is bending rigidity, the numerical value
Less, fabric is more easily bent, and flexibility is better.
Fabric whiteness is tested using WSB-2 types numeral measuring brightness instrument, and the meansigma methodss of parallel 5 tests are most to terminate
Really.
Fabric water absorption testing 1mL standard droppers are from the fabric face drop sprawled to level at fabric 3cm height
One drop water, has absorbed 1 and has dripped the time used with stopwatch record fabric under quiescent conditions, and the meansigma methodss of parallel 5 tests are
Final result.
Contact angle of the hydrophobicity water of fabric on its surface is represented, surveyed using JC2000C type Static Contact angle measuring instrument
It is fixed.Test temperature is (22 ± 2) DEG C, and liquid infusion volume is 5 μ L.
The measurement result of fabric application performance is as shown in table 1.
Application performance before and after the Cotton Fabric of table 1
Can be seen that compared to untreated blank bafta, Jing silicone oil PHMS-APE-AN and PHMS- from data in table 1
The flexibility of the bafta that AGE-AN is arranged all improves (bending stiffness is less) than non-finishing of cotton textiles, and the commercially available organosilicons of Jing
The flexibility of the bafta that quaternary ammonium salt antiseptic is arranged then is reduced than non-finishing of cotton textiles.Additionally, commercial antimicrobial agent is processed knitting
The whiteness value of thing is poor with hydrophilic, water absorption, illustrates that this commercial antimicrobial agent is difficult the soft finish separately as bafta
Agent is used.And silicone oil PHMS-APE-AN and PHMS-AGE-AN can be used as the soft finishing agent of bafta, and can
To obtain preferable fabric treating performance by the suitable segmented structure of control and length.
Antibiotic property test and evaluation criterion of the silicone oil with emulsion
This experiment adopts paper disk method, judges silicone oil and emulsion to staphylococcus aureuses (25923) and escherichia coli
(TOP10) anti-microbial property of two strains.Specific experiment operating procedure is as follows:
1st, ultra violet lamp 30min；
2nd, alcohol burner is lighted, super-clean bench, handss are wiped；
3rd, the little scraps of paper of distribution add 5 μ L samples on the scraps of paper in plate, respectively；
4th, in the clean flat board of mean allocation each sample position；
5th, respectively staphylococcus aureuses (25923), escherichia coli (TOP10) are inoculated in into clean LB culture medium flat plates
Upper (LB culture medium：Peptone 10g, yeast extract 5g, NaCl 5g, agar 15g, distilled water 1L, pH=7.0)；
6th, the little scraps of paper for scribbling sample are affixed on into corresponding position in the flat board containing antibacterial；
7th, put in 37 DEG C of incubator and cultivate.
The evaluation criterion of antibacterial effect such as table 2：
The antibacterial effect evaluation criterion of table 2
The test result such as table 3 of silicone oil and emulsion antibacterial effect：
The silicone oil of table 3 and corresponding emulsion to large intestine TOP10 strains and
The antibacterial circle diameter of staphylococcus aureuses ATCC 25923
Silicone oil is can be seen that from data in table 3 all to have large intestine TOP10 strains and staphylococcus aureuses ATCC25923
There is preferable antibiotic property, 20mm may each be about to the antibacterial circle diameter of both strains, the antibacterial circle diameter of commercial antimicrobial agent is maximum,
This quaternary amine quaternary amines content higher with its intramolecular is relevant.Silicone oil is made into after emulsion is diluted, corresponding antibacterial circle diameter
Diminish.
The antibiotic property test of bafta after arrangement
Evaluation 1st of the anti-microbial property test method of fabric with reference to GB/T 20944.1-2007 antibacterial textile performances
Point agar diffusion method is carried out, and selects aliquot part, and every kind of bacterium tests 4 pieces (positive and negative is each 2 pieces), sample according to diameter 25mm ±
5mm is cut into circle.With 100% bafta as control sample.(18-24) h is cultivated at 37 DEG C ± 2 DEG C.Main operational steps are such as
Under：
1st, prepare lower floor's aseptic culture medium, 10mL agar culture mediums are poured into in sterilized petri dishes, make condensation.
2nd, upper strata inoculation medium is prepared.45 DEG C of ± 2 DEG C of agar culture medium 150mL are put into flask, add 1mL bacterium solutions, shake
Swinging flask mixes bacterium solution, and in each lower floor's aseptic culture medium 5mL is poured into, and condenses it.
3rd, sample and control sample are put in respectively in plate with aseptic nipper, allow sample to be fully contacted with agar culture medium.
It is put into 37 DEG C ± 2 DEG C of incubator culture 18-24h.
The test result of bafta antibacterial effect such as table 4：
The anti-microbial property test result of bafta after the arrangement of table 4
It is found that compared to untreated blank bafta, Jing silicone oil PHMS-APE-AN and PHMS-AGE- from table 4
The bafta that AN emulsions are arranged all has certain antibacterial to large intestine TOP10 strains and staphylococcus aureuses ATCC 25923
Property, the bafta that wherein Jing PHMS1-APE-AN, PHMS2-APE-AN and PHMS1-AGE-AN, PHMS2-AGE-AN emulsions are arranged
Antibacterial bandwidth be both greater than 1mm.And have a large amount of bacterium colonies on blank bafta, without antibacterial bandwidth.The agent of Jing commercial antimicrobials is arranged
Fabric also without bacterial reproduction, but antibacterial bandwidth is zero, it may be possible to it is relatively low with consumption relevant.
The durability test of bafta antibacterial effect after arrangement
With reference to GB BG 8629-2001, with commercially available carving board detergent cleaning mixture (4g/L, bath raio 1 are made into:30), water temperature 30
± 3 DEG C, fabric is put in washing machine under room temperature stirs 10min, then rinsed in clear water, as once washing.Drying cotton
After fabric, its anti-microbial property is tested.
Antibacterial tests operating procedure is as follows：
1st, strain inoculation will preserve strain transferred species 2 times, and standby antibacterial experiment is used.
2nd, well-grown strain normal saline dilution is to convenient multiple after bacteria suspension is prepared and will transferred in super-clean bench.
3rd, it is down flat plate and pours culture medium into flat board in super-clean bench, per plate about 25mL or so, horizontal positioned is inverted after solidification
In being put into 30 DEG C of incubators, colony growth is seen whether after 2 days, be available for next step experiment to use if not, otherwise needed again
It is down flat plate.
4th, it is coated in super-clean bench and takes 0.1ml bacteria suspensions injection flat board with rifle, places the rear triangle rakes of 5min or so and be coated with
Uniformly.
5th, flat board is equally divided into 4 areas by paster in super-clean bench, will be cut into blockage containing sample gauze, point positive and negative
It is attached on flat board, one matched group of per group of setting.
6th, it is put in 37 DEG C of constant temperature biochemical cultivation cases and cultivates observation experiment result after 12h.
The durability test result of bafta antibacterial effect such as table 5：
The bafta of table 5 wash after anti-microbial property test result
From table 5 it is found that after once washing, the fungistatic effect of bafta has generally declined after arrangement, suppression
Bacterium loop diameter is decreased obviously, the corresponding bafta antibacterial circle diameter ＞ of only silicone oil PHMS1-APE-AN and PHMS2-APE-AN
1mm.But in addition to the blank bafta of control sample has a large amount of colony growths, what each group fabric samples Jing antibacterials silicone oil emulsion was arranged
There is not breeding colony phenomenon in surface of cotton fabric, although the finishing of cotton textiles fungistatic effect after showing to wash have dropped, but still
It is with fungistatic effect.
Claims (9)
1. a kind of N, the quaternised modified silicone oil in N- dimethyl dodecyl bases end, it is characterised in that containing structure as shown in formula I
Compound：
In formula I, it is that 0～5, b is 0～20 that n is 7～100, a.
2. a kind of N as claimed in claim 1, the preparation method of the quaternised modified silicone oil in N- dimethyl dodecyl bases end, its
It is characterised by, comprises the steps：
1) octamethylcy-clotetrasiloxane and hydrogeneous double-seal head carry out polyreaction under acidic catalyst effect, obtain holding Silicon Containing Hydrogen
Oil；
The structure of the end containing hydrogen silicone oil is as shown in formula II：
In formula II, n is 7～100；
2) by step 1) in the end containing hydrogen silicone oil that obtains contract with allyl glycidyl ether or allyl polyethenoxy polyoxypropylene
Water glycerin ether carries out hydrosilylation, obtains holding epoxy silicon oil；
The structure of the end epoxy silicon oil is as shown in formula III：
In formula III, it is that 0～5, b is 0～20 that n is 7～100, a；
3) by step 2) in the end epoxy silicon oil that obtains and N, N- dimethyl dodecylamine and acetic acidreaction, obtain the N, N-
The quaternised modified silicone oil in dimethyl dodecyl base end.
3. N according to claim 2, the preparation method of the quaternised modified silicone oil in N- dimethyl dodecyl bases end, it is special
Levy and be, the step 1) in acidic catalyst be Emathlite or H2SO4。
4. N according to claim 2, the preparation method of the quaternised modified silicone oil in N- dimethyl dodecyl bases end, it is special
Levy and be, the step 1) in the mass ratio of octamethylcy-clotetrasiloxane and hydrogeneous double-seal head be 4～75:1.
5. N according to claim 2, the preparation method of the quaternised modified silicone oil in N- dimethyl dodecyl bases end, it is special
Levy and be, the step 1) in reaction temperature be 60～80 DEG C, the response time is 5～24h.
6. N according to claim 2, the preparation method of the quaternised modified silicone oil in N- dimethyl dodecyl bases end, it is special
Levy and be, the step 2) middle-end containing hydrogen silicone oil shrinks sweet with allyl glycidyl ether or allyl polyethenoxy polyoxypropylene
The mol ratio of oily ether is 1:2～2.2.
7. N according to claim 2, the preparation method of the quaternised modified silicone oil in N- dimethyl dodecyl bases end, it is special
Levy and be, the step 2) in reaction temperature be 60～90 DEG C, the response time is 3～12h.
8. N according to claim 2, the preparation method of the quaternised modified silicone oil in N- dimethyl dodecyl bases end, it is special
Levy and be, the step 3) in reaction temperature be 60～90 DEG C, the response time is 3～12h.
9. a kind of N as claimed in claim 1, the quaternised modified silicone oil in N- dimethyl dodecyl bases end is preparing textile finishing
Application in agent.
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| CN113683536B (en) * | 2021-08-19 | 2023-01-13 | 浙江三元纺织有限公司 | Preparation of betaine type quaternary ammonium salt antibacterial agent and method for applying same to fabric finishing |
| CN116003805A (en) * | 2023-02-20 | 2023-04-25 | 常州市中策纺织助剂有限公司 | Preparation method of anionic block silicone oil |
| CN116003805B (en) * | 2023-02-20 | 2024-01-30 | 常州市中策纺织助剂有限公司 | Preparation method of anionic block silicone oil |
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